Use of at least trivalent alcohols and their alkoxylation products increasing the speed of dissolution of particulate detergent formulations in water

ABSTRACT

The use of at least trihydric alcohols and their reaction products with ethylene oxide and/or propylene oxide as additive to particulate detergent formulations, especially compact detergents, to increase their rate of dissolving in water in amounts of from 0.1 to 5% by weight based on the detergent formulations.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the use of at least trihydric alcohols andtheir reaction products with ethylene oxide and/or propylene oxide asadditive to particulate detergent formulations to increase their rate ofdissolving in water in amounts of from 0.1 to 5% by weight based on thedetergent formulations.

2. Description of the Background

Particulate detergents are intended, on introduction into water, todisintegrate as quickly as possible into-the individual ingredients inorder to form the wash liquor ready for use. The rate of dissolving ofsome particulate detergent formulations, in particular compactdetergents which have, for example, an apparent density of at least 550g/l, on mixing with water is, however, still in need of improvement.

It is an object of the present invention to provide a detergent additivewhich results in an increase in the rate of dissolving of particulatedetergents in water.

SUMMARY OF THE INVENTION

We have found that this object is achieved by the use of reactionproducts of at least trihydric alcohols with ethylene oxide and/orpropylene oxide as additive to particulate detergent formulations toincrease their rate of dissolving in water in amounts of from 0.1 to 5%by weight based on the detergent formulations.

DETAILED DESCRIPTION OF THE INVENTION

Examples of suitable at least trihydric alcohols are glycerol,diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol,heptaglycerol and octaglycerol, pentaerythritol, trimethylolpropane,erythritol, mannitol, sorbitol, sucrose, glucose and polyvinyl alcoholswith molecular weights of up to 20,000. In place of the individualcompounds it is also possible to employ mixtures of said compounds. Ofparticular industrial interest is, for example, the use of hydrogenatedstarch hydrolyzates or hydrogenated glucose syrups. It is possible toemploy, for example, commercially available hydrogenated starchhydrolyzates supplied by Cerestar under the trade names SORBIDEX 200 andSORBIDEX 122.

Particularly effective products for increasing the rate of dissolving ofparticulate detergent formulations are reaction products of at leasttrihydric alcohols with ethylene oxide and/or propylene oxide. Thesereaction products and processes for their preparation form part of theprior art. Thus, for example, reaction of glycerol, erythritol,pentaerythritol, trimethylolpropane, mannitol or sorbitol with ethyleneoxide and/or propylene oxide in the presence of conventionalalkoxylation catalysts such as KOH, NaOH, Ca hydroxide, Ca oxide orsupported catalysts results in detergent additives which considerablyincrease the rate of dissolving of detergent formulations in watercompared with polyethylene glycol. The alkoxylated products may have awide or a narrow molecular weight distribution. Of particular importancein this connection are the reaction products of glycerol, erythritol,pentaerythritol, trimethylolpropane, mannitol or sorbitol with ethyleneoxide. For example, 1 mol of an at least trihydric alcohol is reactedwith 1 to 100 mol of ethylene oxide. These products can be modified byallowing them to react further where appropriate with up to 20 mol ofpropylene oxide. However, the procedure for preparing modified ethyleneoxide adducts can be such that a mixture of ethylene oxide and propyleneoxide gases is allowed to act on the at least trihydric alcohols.Another possible variation comprises reacting said alcohols initiallywith propylene oxide and subsequently with ethylene oxide. Propyleneoxide is preferably employed in an amount of from 1 to 15 mol per moleof alcohol. Reaction products of 1 mol of trimethylolpropane with 1 to100 mol of ethylene oxide are particularly preferably employed, withreaction products of 1 mol of trimethylolpropane with 3 to 30 mol ofethylene oxide mostly being used.

Also suitable as detergent additive which increases the rate ofdissolving of detergent formulations in water are ethoxylatedhydrogenated sugars such as sorbitol or mannitol, and ethoxylatedpolyvinyl alcohol. The additives to be used according to the inventionare present in the detergent formulation in amounts of from 0.1 to 5,preferably 0.5 to 2,% by weight. They are preferably mixed ashomogeneously as possible with the other detergent ingredients. However,they can also be applied to the surface of the fine-particle detergentformulations and allowed to diffuse in.

The detergents can be in powder form or in the form of granules, flakes,pellets, beads, plates or tablets. The average particle diameter of theparticulate detergent formulations is, for example, 200 μm to 5 mm andis preferably in the range from 1 to 3 mm. However, the detergentformulations can also be portioned in such a way that only one bead orone tablet is necessary for one wash in a washing machine. Beads ortablets of this type then have a far larger average particle diameterthan indicated above. The advantage of such relatively large-volumeparticles is that dosage is easy.

The detergents may be heavy duty detergents or speciality detergents.Suitable surfactants are both anionic and nonionic or mixtures ofanionic and nonionic surfactants. The surfactant content of thedetergents is preferably 8 to 30% by weight.

Examples of suitable anionic surfactants are fatty alcohol sulfates fromfatty alcohols with 8 to 22, preferably 10 to 18, carbon atoms, e.g. C₉-C₁₁ -alcohol sulfates, C₁₂ -C₁₃ -alcohol sulfates, cetyl sulfate,myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fattyalcohol sulfate.

Other suitable anionic surfactants are sulfated, ethoxylated C₈ -C₂₂-alcohols and their soluble salts. Compounds of this type are prepared,for example, by initially alkoxylating a C₈ -C₂₂ -, preferably a C₁₀-Cl₈ -, alcohol and subsequently sulfating the alkoxylation product.Ethylene oxide is preferably used for the alkoxylation, employing 2 to50, preferably 3 to 20, mol of ethylene oxide per mole of fatty alcohol.However, the alcohols can also be alkoxylated with propylene oxide,alone or with butylene oxide. Also suitable are those alkoxylated C₈-C₂₂ -alcohols which contain ethylene oxide and propylene oxide orethylene oxide and butylene oxide. The alkoxylated C₈ -C₂₂ -alcohols maycontain the ethylene oxide, propylene oxide and butylene oxide units inthe form of blocks or in random distribution.

Other suitable anionic surfactants are alkylsulfonates such as C₈ -C₂₄-, preferably C₁₀ -C₁₈ -, alkanesulfonates, and soaps such as the saltsof C₈ -C₂₄ -carboxylic acids. Other suitable anionic surfactants arelinear C₉ -C₂₀ -alkylbenzenesulfonates (LAS). The polymers according tothe invention are preferably employed in detergent formulations with anLAS content of less than 4%, particularly preferably in LAS-freeformulations.

The anionic surfactants are added to the detergent preferably in theform of salts. Suitable cations in these salts are alkali metal ionssuch as sodium, potassium, lithium and ammonium ions, e.g.hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium ions.

Examples of suitable nonionic surfactants are alkoxylated C₈ -C₂₂-alcohols. The alkoxylation can be carried out with ethylene oxide,propylene oxide and/or butylene oxide. It is possible to employ assurfactant in this case all alkoxylated alcohols which contain at leasttwo molecules of an abovementioned alkylene oxide in the adduct. Alsosuitable in this connection are block copolymers of ethylene oxide,propylene oxide and/or butylene oxide, or adducts which contain saidalkylene oxides in random distribution. 2 to 5, preferably 3 to 20, molof at least one alkylene oxide are employed per mole of alcohol.Ethylene oxide is preferably employed as alkylene oxide. The alcoholspreferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants comprises alkyl polyglucosideswith 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain.These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.

Another class of nonionic surfactants comprises N-alkylglucamides of thegeneral structure I or II ##STR1## where A is C₆ -C₂₂ -alkyl, B is H orC₁ -C₄ -alkyl and C is a polyhydroxyalkyl radical with 5 to 12 carbonatoms and at least 3 hydroxyl groups. A is preferably C₁₀ -C₁₈ -alkyl, Bis preferably CH₃ and C is preferably a C₅ or C₆ radical. Compounds ofthis type are obtained, for example, by acylation of reductivelyaminated sugars with chlorides of C₁₀ -C₁₈ -carboxylic acids. Thedetergent formulations preferably contain C₁₀ -C₁₆ -alcohols ethoxylatedwith 3-12 mol of ethylene oxide, particularly preferably ethoxylatedfatty alcohols, as nonionic surfactants.

Other suitable and preferred surfactants are the endgroup-capped fattyamide alkoxylates, which are disclosed in WO-A-95/11225, of the generalformula

    R.sup.1 --CO--NH--(CH.sub.2).sub.n --O--(AO).sub.x --R.sup.2 (III),

where

R¹ is C₅ -C₂₁ -alkyl or -alkenyl,

R² is C₁ -C₄ -alkyl,

A is C₂ -C₄ -alkylene,

n is 2 or 3, and

x has a value from 1 to 6.

Examples of such compounds are the reaction products ofn-butyltriglycolamine of the formula H₂ N--(CH₂ --CH₂ --O)₃ --C₄ H₉ withmethyl dodecanoate or the reaction products of ethyltetraglycolamine ofthe formula H₂ N--(CH₂ --CH₂ --O)₄ --C₂ H₅ with a commercial mixture ofsaturated C₈ -C₁₈ fatty acid methyl esters.

The detergents in powder or granule form additionally contain one ormore inorganic builders. Suitable inorganic builders are allconventional inorganic builders such as alumosilicates, silicates,carbonates and phosphates. Examples of suitable inorganic builders arealumosilicates with ion-exchanging properties such as zeolites. Varioustypes of zeolites are suitable, in particular zeolites A, X, B, P, MAPand HS in their Na form or in forms in which Na is partly replaced byother cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites aredescribed, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087035, U.S. Pat. No. 4,604,224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384070A and WO-A-94/24251.

Other suitable inorganic builders are, for example, amorphous orcrystalline silicates such as amorphous disilicates, crystallinedisilicates such as the sheet silicate SKS-6 (manufactured by HoechstAG). The silicates can be employed in the form of their alkali metal,alkaline earth metal or ammonium salts. Na, Li and Mg silicates arepreferably employed.

Other suitable inorganic builders are carbonates and bicarbonates. Thesecan be employed in the form of their alkali metal, alkaline earth metalor ammonium salts. Na, Li and Mg carbonates and bicarbonates, inparticular sodium carbonate and/or sodium bicarbonate, are preferablyemployed.

The inorganic builders can be present in the detergents in amounts offrom 0 to 60% by weight together with organic cobuilders to be usedwhere appropriate. The inorganic builders can be incorporated into thedetergent either alone or in any combination with one another. They areadded to detergents in powder or granule form in amounts of from 10 to60% by weight, preferably in amounts of from 20 to 50% by weight.

Detergent formulations in powder or granule form or other solidformulations contain organic cobuilders in amounts of from 0.1 to 20% byweight, preferably in amounts of from 1 to 15% by weight, together withinorganic builders. The heavy duty 10 detergents in powder or granuleform may additionally contain as other conventional ingredients a bleachsystem consisting of at least one bleach, where appropriate combinedwith a bleach activator and/or a bleach catalyst.

Suitable bleaches are perborates and percarbonates in the form of theiralkali metal, in particular their Na, salts. They are present in theformulations in amounts of from 5 to 30% by weight, preferably 10 to 25%by weight. Other suitable bleaches are inorganic and organic peracids inthe form of their alkali metal or magnesium salts or partly also in theform of the free acids. Examples of suitable organic peracids and saltsthereof are Mg monoterephthalate, phthalimidopercaproic acid anddiperdodecanedioic acid. An example of an inorganic peracid salt ispotassium peroxomonosulfate (Oxon).

Examples of suitable bleach activators are

acylamine such as tetraacetylethylenediamine, tetraacetylglycoluril,N,N'-diacetyl-N,N'-dimethylurea and1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine

acylated lactams such as acetylcaprolactam, octanoylcaprolactam andbenzoylcaprolactam

substituted phenol esters of carboxylic acids such as Naacetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Nanonanoyloxybenzenesulfonate

acylated sugars such as pentaacetylglucose

anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil

enol esters such as isopropenyl acetate

oxime esters such as acetone 0-acetyloxime

carboxylic anhydrides such as phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates arepreferably employed as bleach activators. The bleach activators areadded to heavy duty detergents in amounts of from 0.1 to 15% by weight,preferably in amounts of from 1.0 to 8.0% by weight, particularlypreferably in amounts of from 1.5 to 6.0% by weight.

Suitable bleach catalysts are quaternized imines and sulfone imines asdescribed in U.S. Pat. No. 5,360,568, U.S. Pat. No. 5,360,569 and EP-A-0453 003, and Mn complexes, cf., for example, WO-A-94/21777. If bleachcatalysts are employed in the detergent formulations, they are presenttherein in amounts of up to 1.5% by weight, preferably up to 0.5% byweight, and in the case of the very active manganese complexes inamounts of up to 0.1% by weight.

The detergents preferably contain an enzyme system. This comprisesproteases, lipases, amylases and cellulases normally employed indetergents. The enzyme system may be restricted to a single one of theenzymes or contain a combination of different enzymes. The amounts ofcommercial enzymes added to the detergents are, as a rule, from 0.1 to1.5% by weight, preferably 0.2 to 1.0% by weight of the formulatedenzyme. Examples of suitable proteases are Savinase and Esperase(manufactured by Novo Nordisk). An example of a suitable lipase isLipolase (manufactured by Novo Nordisk). An example of a suitablecellulase is Celluzym (manufactured by Novo Nordisk).

The detergents preferably contain as other conventional ingredients soilrelease polymers and/or antiredeposition agents. These are, for example,

polyesters from polyethylene oxides with ethylene glycol and/orpropylene glycol and aromatic dicarboxylic acids or aromatic andaliphatic dicarboxylic acids. Polyesters from polyethylene oxides whichare endgroup-capped at one end with di- and/or polyhydric alcohols anddicarboxylic acids. Polyesters of these types are known, cf., forexample, U.S. Pat. No. 3,557,039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0241 984, EP-A-0 241 985, EP-A-0 272 033 and U.S. Pat. No. 5,142,020.

Other suitable soil release polymers are amphiphilic graft or othercopolymers of vinyl and/or acrylic esters on polyalkylene oxides, cf.U.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-3 711 299, U.S.Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126or modified celluloses such as methylcellulose, hydroxypropylcelluloseor carboxymethylcellulose.

Antiredeposition agents and soil release polymers are present in thedetergent formulations in amounts of 0 to 2.5% by weight, preferably 0.2to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight. Soilrelease polymers which are preferably employed are the graft copolymers,disclosed in U.S. Pat. No. 4,746,456, of vinyl acetate on polyethyleneoxide of molecular weight 2500-8000 in the ratio 1.2:1 to 3.0:1 byweight, and commercial polyethylene terephthalate/polyoxyethyleneterephthalates of molecular weight 3000 to 25000 from polyethyleneoxides of molecular weight 750 to 5000 with terephthalic acid andethylene oxide and a molar ratio of polyethylene terephthalate topolyoxyethylene terephthalate of 8:1 to 1:1, and the blockpolycondensates, disclosed in DE-A-4 403 866, which contain blocks of(a) ester units from polyalkylene glycols with a molecular weight of 500to 7500 and aliphatic dicarboxylic acids and/or monohydroxy carboxylicacids and (b) ester units from aromatic dicarboxylic acids andpolyhydric alcohols. These amphiphilic block copolymers have molecularweights of from 1500 to 25000.

A typical heavy duty detergent in powder or granule form can have thefollowing composition, for example:

3-50, preferably 8-30,% by weight of at least one anionic and/ornonionic surfactant,

5-50, preferably 15-42.5, % by weight of at least one inorganic builder,

5-30, preferably 10-25, % by weight of an inorganic bleach,

0.1-15, preferably 1-8, % by weight of a bleach activator,

0-1, preferably up to a maximum of 0.5, % by weight of a bleachcatalyst,

0.05-5% by weight, preferably 0.2-2.5% by weight, of a color transferinhibitor based on water-soluble homopolymers of N-vinylpyrrolidone orN-vinylimidazole, water-soluble copolymers of N-vinylimidazole andN-vinylpyrrolidone, crosslinked copolymers of N-vinylimidazole andN-vinylpyrrolidone with a particle size of from 0.1 to 500, preferablyup to 250, μm, these copolymers containing 0.01 to 5, preferably 0.1 to2, % by weight of N,N'-divinylethyleneurea as crosslinker. Other colortransfer inhibitors are water-soluble and crosslinked polymers of4-vinylpyridine N-oxide obtainable by polymerizing 4-vinylpyridine andsubsequently oxidizing the polymers,

0.1-20, preferably 1-15, % by weight of at least one modifiedpolyaspartic acid to be used according to the invention as organiccobuilder,

0.2-1.0% by weight of protease,

0.2-1.0% by weight of lipase,

0.3-1.5% by weight of a soil release polymer.

A bleach system is often entirely or partly dispensed with within mildspeciality detergents (for example in color detergents). A typical colordetergent in powder or granule form may, for example, have the followingcomposition:

3-50, preferably 8-30, % by weight of at least one anionic and/ornonionic surfactant,

10-60, preferably 20-55, % by weight of at least one inorganic builder,

0-15, preferably 0-5, % by weight of an inorganic bleach,

0.05-5% by weight, preferably 0.2-2.5, % by weight of a color transferinhibitor, cf. above,

0.1-20, preferably 1-15, % by weight of at least one modifiedpolyaspartic acid described above as organic cobuilder,

0.2-1.0% by weight of protease,

0.2-1.0% by weight of cellulase,

0.2-1.5% by weight of a soil release polymer, e.g. a graft copolymer ofvinyl acetate on polyethylene glycol.

The detergents in powder or granule form can contain as otherconventional ingredients up to 60% by weight of inorganic fillers.Sodium sulfate is normally used for this purpose. However, thedetergents preferably have a low filler content, i.e. they contain up to20% by weight, particularly preferably up to 8% by weight, of fillers.The detergents may have apparent densities varying in the range from 300to 1000 g/l. Modern compact detergents as a rule have high apparentdensities, e.g. 550 to 1000 g/l, and a granular structure.

The detergents may, where appropriate, contain other conventionaladditives. Other additives which may be present where appropriate are,for example, complexing agents, phosphonates, optical brighteners, dyes,perfume oils, foam suppressants and corrosion inhibitors. They mayadditionally contain up to 20% by weight of water.

EXAMPLE 1

25 g of commercial Persil® Megaperls are stirred with 3.5 g of water at60° C. to give a paste and intimately mixed with 0.5 g of an adduct of10 mol of ethylene oxide and 1 mol of trimethylolpropane. A bead isformed from 1.00 g of the paste obtainable in this way. The timenecessary for complete disintegration of the bead into the individualingredients to form a wash liquor is then determined by stirring thebead in 500 ml of water at 30° C. using a magnetic stirrer at 500 rpm.The bead had completely disintegrated into the individual ingredients toform a wash liquor after 27 min.

EXAMPLE 2

Example 1 is repeated with the sole exception that the adduct of 30 molof ethylene oxide and 1 mol of trimethylolpropane is employed as agentto increase the rate of dissolving. After the bead formed from themixture had been stirred at 500 rpm in 500 ml of water at 30° C. for 29minutes the bead had completely disintegrated into the individualingredients to form a wash liquor.

COMPARATIVE EXAMPLE 1

25 g of commercial Persil® Megaperls are stirred with 3.5 g of water at60° C. to give a paste. A bead is formed from 1.00 g of this mixture andthen the time necessary for complete disintegration of the bead into theindividual ingredients to form a wash liquor is determined as indicatedin Example 1. 35 min was required for this.

COMPARATIVE EXAMPLES 2 to 6

The procedure is as described in Example 1 but, in place of the adductof ethylene oxide and trimethylolpropane employed therein, the ethyleneoxide derivatives indicated in the table are used.

The time necessary for complete disintegration of the bead into theindividual ingredients to form a wash liquor is likewise indicated inthe table.

                  TABLE                                                           ______________________________________                                                                      Time [min] for complete                                 Ethylene              disintegration of the                           Comparative                                                                           oxide       Molecular bead formed from the                            Example derivative  weight M.sub.N                                                                          mixture                                         ______________________________________                                        2       Polyethylene                                                                              300       31                                                      glycol                                                                3       Polyethylene                                                                              600       32                                                      glycol                                                                4       Polyethylene                                                                              1500      34                                                      glycol                                                                5       Polyethylene                                                                              4000      32                                                      glycol                                                                6       Adduct of             34                                                      34 mol                                                                        ethylene                                                                      oxide and                                                                     1 mol C.sub.13 /C.sub.15                                                      alcohol                                                               ______________________________________                                    

We claim:
 1. A particulate detergent formulation which contains from 0.1to 5% by weight of a reaction product of 1 mol of at least onepolyhydric alcohol containing at least three hydroxyl groups with 1 to100 mol of ethylene oxide and optionally, with up to 20 mol of propyleneoxide, wherein the reaction product increases the rate of dissolution ofthe formulation in water.
 2. The particulate detergent formulation asclaimed in claim 1 wherein the polyhydric alcohol comprises glycerol,erythritol, pentaerythritol, trimethylolpropane, mannitol or sorbitol.3. The particulate detergent formulation as claimed in claim 1, whereinthe reaction product comprises the reaction product of 1 mol oftrimethylolpropane with 1 to 100 mol of ethylene oxide.
 4. Theparticulate detergent formulation as claimed in claim 1, wherein thereaction product comprises the reaction product of 1 mol oftrimethylolpropane with 3 to 30 mol of ethylene oxide.
 5. Theparticulate detergent formulation as claimed in claim 1, comprising 0.5to 2.5% by weight, based on the weight of the detergent formulation, ofthe reaction products.
 6. The particulate detergent formulation asclaimed in claim 1, having an apparent density of from 550 to 1000 g/l.7. The particulate detergent formulation as claimed in claim 1, havingan apparent density of at least 700 g/l.